[2-[二甲基-(2-甲基苯基)甲硅烷基]苯基]甲醇 | 853955-71-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: [2-[二甲基-(2-甲基苯基)甲硅烷基]苯基]甲醇
• 中文别名: 2-[(2-甲基苯基)二甲基硅基]苯甲醇
• 英文名称: [2-(hydroxymethyl)phenyl]dimethyl(2-methylphenyl)silane
• 英文别名: {2-[Dimethyl(2-methylphenyl)silyl]phenyl}methanol；[2-[dimethyl-(2-methylphenyl)silyl]phenyl]methanol
• CAS: 853955-71-2
• 化学式: C₁₆H₂₀OSi
• 分子量: 256.42
• InChiKey: VNMCFSBIGQPPOE-UHFFFAOYSA-N

物化性质

• 密度：
  1.03g/ml

计算性质

• 辛醇/水分配系数(LogP)：
  2.31
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [2-[二甲基-(2-甲基苯基)甲硅烷基]苯基]甲醇 、 二氧化碳 在 copper(l) iodide 、 cesium fluoride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 20.0h， 以72%的产率得到对甲苯甲酸
  参考文献：
  名称：

  未活化的芳基和烯基硅烷与二氧化碳的铜催化羧化

  摘要：

  通过有机硅烷与二氧化碳的铜催化羧化反应，开发了一种用于制备芳基和烯基羧酸的温和合成方案。关键...

  DOI：

  10.1246/cl.190577
• 作为产物：
  描述：

  dimethyl[2-(2-tetrahydro-2H-pyranoxymethyl)phenyl]silane 在 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 16.0h， 生成 [2-[二甲基-(2-甲基苯基)甲硅烷基]苯基]甲醇
  参考文献：
  名称：

  Alkenyl- and Aryl[2-(hydroxymethyl)phenyl]dimethylsilanes:  An Entry to Tetraorganosilicon Reagents for the Silicon-Based Cross-Coupling Reaction

  摘要：

  Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes, highly stable tetraorganosilicon reagents, are found to react with aryl and alkenyl iodides in the presence of a palladium catalyst and K2CO3 as a base, significantly milder conditions compared with those ever reported for the silicon-based cross-coupling reactions. The reaction tolerates a wide range of functional groups, including silyl protectors, and allows a gram-scale synthesis to recover and reuse the silicon residue.

  DOI：

  10.1021/ja051281j

文献信息

• Synthesis of Biaryls and Oligoarenes Using Aryl[2-(hydroxymethyl)phenyl]dimethylsilanes
  作者：Jinshui Chen、Masaaki Tanaka、Akhila K. Sahoo、Masahide Takeda、Akira Yada、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1246/bcsj.20090325

  日期：2010.5.15

  Through intramolecular activation, highly stable aryl[2-(hydroxymethyl)phenyl]dimethylsilanes can selectively transfer their aryl groups to effect a cross-coupling reaction with various aryl bromides and chlorides in the presence of a weak non-fluoride base and a palladium/copper catalyst. This reaction tolerates a wide range of functional groups, producing the corresponding functionalized biaryls in high yields with excellent chemoselectivity. Newly disclosed reaction conditions allow the recovery of a cyclic silyl ether in modest-to-good yields and reuse for the synthesis of the arylsilanes. The introduction of two isopropyl groups on the silicon center instead of methyl groups improves the stability and allows quantitative recovery of the silicon residue. Finally, aryl halides having an O-protected [2-(hydroxymethyl)phenyl]dimethylsilyl group cross-couple with the arylsilane reagents to give silyl-functionalized biaryls. Upon deprotection, the biaryls further react with the silylated electrophiles. The iterative cross-coupling–deprotection sequences allow rapid assembly of silylated oligoarenes. Syntheses of di- and trisilyloligoarenes are also achieved by use of orthogonal O-protecting groups.

  通过分子内活化，高度稳定的二甲基[2-（羟甲基）苯基]硅烷可以将其苯基选择性地转移到各种含有苯基卤化物的芳基溴化物和氯化物上，在非氟化弱碱和钯/铜催化剂的存在下进行交联反应。该反应耐受广泛的功能基团，以高产率和高化学选择性生成相应的功能化双芳基化合物。新披露的反应条件允许以中等至良好的产率回收环状硅醚，并可重复使用于合成芳基硅烷。在硅中心引入两个异丙基取代甲基可提高稳定性，并能定量回收硅残基。最后，拥有保护性O-[2-（羟甲基）苯基]二甲基硅烷基团的芳基卤化物与芳基硅烷反应剂交联，生成含硅功能化双芳基化合物。去保护后，双芳基化合物再与硅化亲电试剂反应。通过交叉耦合-去保护序列的迭代，可以快速组装含硅的寡芳烃。通过使用正交氧保护基团，还可以实现二硅和三硅寡芳烃的合成。
• Carboallylation of electron-deficient alkenes by palladium/copper catalysis
  作者：Kazuhiko Semba、Naoki Ohta、Yuko Yano、Yoshiaki Nakao

  DOI：10.1039/c8cc06023a

  日期：——

  A method for the carboallylation of electron-deficient alkenes with tetraorganosilicon reagents and allylic carbonates based on Pd/Cu catalysis has been developed. This method affords a wide range of structurally diverse carbon skeletons from readily available starting materials, and tolerates various functional groups.

  开发了一种基于Pd / Cu催化的四有机硅试剂和烯丙基碳酸酯将缺电子烯烃进行碳烯丙基化的方法。该方法从容易获得的起始原料中提供了多种结构多样的碳骨架，并且可以耐受各种官能团。
• Copper-Catalyzed Electrophilic Amination of Arylsilanes with Hydroxylamines
  作者：Yuya Miki、Koji Hirano、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/ol303222s

  日期：2013.1.4

  A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl]dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.

  已经开发出铜催化的芳基[（2-羟甲基）苯基]二甲基硅烷与O-酰化的羟胺的亲电胺化，以良好的产率提供相应的苯胺。催化反应在温和条件下进行得非常顺利，并能耐受各种官能团。
• Rhodium-catalyzed Addition of Organo[2-(hydroxymethyl)phenyl]dimethylsilanes to Arenesulfonylimines
  作者：Yoshiaki Nakao、Masahide Takeda、Jinshui Chen、Tamejiro Hiyama、Yoshitaka Ichikawa、Ryo Shintani、Tamio Hayashi

  DOI：10.1246/cl.2008.290

  日期：2008.3.5

  The title reaction is found to proceed in the presence of a rhodium/diene catalyst. Variously substituted diarylmethylamines and allylamines having an N-arenesulfonyl protection are obtained in good yields, which are important building blocks in organic synthesis.

  该反应发现可以在铑/二烯催化剂的存在下进行。多种取代的二芳基甲基胺和具有N-芳磺酰保护的烯丙胺以良好的产率获得，这些都是有机合成中的重要构建块。
• Rhodium-Catalyzed Hydroarylation and Hydroalkenylation of Alkynes Using Organo[2-(hydroxymethyl)phenyl]dimethylsilanes
  作者：Yoshiaki Nakao、Tamejiro Hiyama、Masahide Takeda、Jinshui Chen

  DOI：10.1055/s-2008-1042812

  日期：——

  The title reaction was found to proceed in the presence of a rhodium/1,2-bis(diphenylphosphino)benzene catalyst. Variously substituted arylethenes and 1,3-dienes were obtained in good yields.

  发现标题反应在铑/1,2-双(二苯基膦基)苯催化剂存在下进行。以良好的收率获得了各种取代的芳基乙烯和1,3-二烯。

表征谱图